Photographic color-forming compounds



Patented Aug. 9, 1938 UNITED STATES- PATENT OFFlCE 2,126,337 PHOTOGRAPHIO coma-roams COM-'- POUNDS Leopold D. Mannes, Leopold Godowsky, Jr., and Willard D. Peterson, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application October 14,1936,

Serial No. 105,616

15 Claims.

development has been described in numerous priorpatents. The present invention relates to a process in which the color-forming compound is contained preferably in the developing solution, but might also be in the sensitive material, and forms a dye simultaneously and in situ with the development of the silver image by coupling with the oxidization product of the photographic developer. In U. S. Patent No. 2,039,730, granted May 5, 1936, to L. D. Mannes and L. Godowsky, Jr., there is disclosed the use of hydroxylated diphenyl compounds for'this purpose. The use of other types of compounds was also decribed in application; Serial No. 8,519, of L. D. Mannes and L. Godowsky, Jr.

We have found that certain hydroxy styryl compounds are useful as coupler compounds in photographic developers and form colored images on photographic development. The dyes which we contemplate using consist of hydroxy styrenes substituted at the end of the chain opposite to that at which the aromatic nucleus -is attached, with an unsaturated or saturated aromatic nucleus or with a. heterocyclic nucleus. The hydroxyl group will usually be in the position ortho with respect to the conjugated chain so that the position para with-respect to the hydroxyl group is left free for coupling with'.

the oxidization product of the developer. In some cases, however, the coupling may occur in the position ortho with respect to the hydroxyl group and in this case the hydroxyl group may occur in the position para with respect to the conjugated chain. l

The hydroxy styryl compounds which we use have the following general formula:

in which Y is a hydrogen atom and R is 'a heterocyclic ring or Y and R. together form a. 1161361.;6576116 ring or an aromatic-ring.

The. following compounds which we contem- (Cl. os- -ss) plate using are compounds in which Y is a hydrogen atom and R is a heterocyclic ring:

. In; N'

l-(o-hydroxycinnamenyl) benzothiazole 2-(o-hydroxycinnamenyl) pyridine C HF'N l /CCH=OH Err- S Z-(o-hydroxycinnamenyl) thiazoline OH v o-st-yrylphenol Inthe following compounds Y and R together represent a heterocyclic ring:

5-(o-hydroxybenzal)-2-thiohydantoin S-phenyl5-(o;hydroxybenzal)-2:4-thiazo1idione In the following compound Y and R together represent an aromatic ring:

flii-disalicylalcyclo-hexanone These compounds may be substituted in the aromatic ring with groups including halide, nitro, amino, substituted amino, alkyl, aryl, and carboxyl groups. These groups may be substituted in the ring at any position except ,in most cases the position para with respect to the hvdroxyl group. In certain cases, however, the substituted groups may occur both ortho and para to the hydroxyl group and in this case the coupling with the developer will occur in the position ortho with respect to the hydroxyl group.

As developing agents we contemplate using aromatic amino compounds which function as photographic developers. The compounds preferred for this purpose are para phenylenediamine and its substituted derivatives. These developers may be substituted in the amino groups as well as in the ring with alkyl, ester, or halide groups. The compounds which we prefer to use are dialkyl para phenylene diamines substituted in one amino group, the other amino group remaining unsubstituted. These compounds are ordinarily used in the salt form, such as the hydrochloride or sulfate, since these compounds are more stable than the amines themselves. Developing a ents which may be used include diethyi para "phenylenediamine, monomethyl para phenylcnediamine hydrochloride. and diethyl para phenylenediamine sulfate.

A developing formula which may be used is the following:

A Diethyl para phgnylenediamine hydrochloof course, be varied. Solvents other than acetone, such as alcohols, may also be used.

The colors formed by the compounds of the I present invention on coupling with the oxidization product of the developer in general range from blue to green. The colors of the specific dyes referred to above, as indicated by visual tests, are as follows:

Blue-green. 1 (o-hydroxycinnamenyl) benzothiazole Blue-green 2 (0 hydroxycinnamenyl) pyridine Blue-green. 2 o hydroxycinnamenyl) thiazoline Dark green o-styrylphenol Yellow-green 5-(o-hydroxybenzal) -2-thioh'ydantoin Light green 3 phenyl-5-(o-hydroxybenzal) -2 4-thiazolidione Green 2:6-disalicylalcyclo-hexanone The color of dyes formed from compounds having substituent groups in the ring may vary according to the type of substituent group employed.

Although we have described our invention with particular reference to the use of the coupling compound in the developing solution itself, our invention is in no way limited to this method. As an alternative method, the coupler compound may be incorporated in'the photographic layer before development, or before development and exposure. It may be adsorbed to the sensitive silver halide grain or chemically combined with the sensitive salt; or, in some cases, the silver salt of the coupler compound itself, without halide. may exhibit light sensitivity and coupling properties on development.

Our compounds may be used to form colored photographic images in films, plates, or paper when gelatin or other suitable colloid is used as the carrier for the silver halide constituting the sensitive salt. The emulsion treated to form the colored image may be on one or both sides of the support or in superposed layers on one or both sides of the support. Where two or more layers are used they may be differently sensitized to form natural colored images on development, according to the process described in application, Serial No. 8,516, filed February 27, 1935 by LID. Mannes and L Godowsky, Jr.

What we claim is:

1. A color-forming photographic developer comprising an aromatic amino developing compound containing a primary amino group andan ortho hydroxy styrene coupler compound containing a substituent group in.the 5 Pos tion of the chain, with which the developing compound is capable of reacting on development.

2. A color-forming photographic developer comprising an aromatic amino developing compound containing a primary amino group and a coupler compound having the formula where Y'CR is a structure selected from the class consisting of structures wherein YC-R together represent the atoms necessary to complete an organic ring selected from the class 0011- mula where YO-R is a structure selected from the class consisting of structures wherein Y-C-R together represent the atoms necessary to complete an organic ring selected from the class consisting of heterocyclic rings and carbocyclic rings, and structures wherein Y represents a hydrogen till areassv atom and R represents an organic ring selected from the class consisting of heterocyclic rings'and aromatic rings.

4. A color-forming photographic developer comprising an aromatic amino developing compound containing a primary amino group and 2 t-disalicylalcyclohexanone.

5. A color-forming photographic developer comprising an aromatic amino developing compound containing a primary amino group and an ortho hydroxystyrene compound having a heterocyclic-ring substituent in the ,3 position of the chain.

ii. A color-forming photographic developer comprising an aromatic amino developing compound containing a primary amino group and i- (o-hydroxycinnamenyl) =benzothiazole.

7. A color-forming photographic developer comprising diethyl paraphenylenediamine hydrochloride and 2:ii-disaiicylalcyclohexanone.

8. A photographic image comprising a dye formed by the coupling oi the development prod not of an aromatic amino developing compound containing a primary amino group with an ortho hydroxy styrene containing a substituent group in the c position of the chain.

9. A photographic image comprising a dye formed by the coupling of the oxidation product of an aromatic amino developing compound containing a primary amino group with an crtho hydroxy styrene containing a substituent group in the ,3 position oi the chain. i

ii). A photographic image comprising a dye formed by the coupling of the development product oi an aromatic amino developing compound containing a primary amino group with a compound having the formula where Y-C--R is a structure selected from the class consisting of structures wherein Y-CR together represent the atoms necessary to complete an organic ring selected from the class consisting of heterocyclic rings and carhocyclic rings, and structures wherein Y represents a hydrogen atom and R represents an organic ring selected from the class consisting of heterocyciic rings and aromatic rings.

ii. A photographic image comprising a dye formed by the coupling of the development prodnot of diethyl paraphenylenediamine hydrochloride with a compound having the formula where YC-R is a structure selected from the class consistingof structures wherein Y-CR together represent the atoms necessary to complete an organic ring selected from the class consisting of heterocyc lic rings and carhocyciic rings, and structures wherein Y represents a hydrogen atom and R represents an organic ring selected from the class consisting of heterocyclic rings and aromatic rings.

12. The method of producing a colored photographic image in a gelatino-silver halide emulsion layer which comprises coupling the development product of an aromatic amino developing compound containing a primary amino group with an ortho hydroxy styrene containing a substituent group in the 5 position of the chain.

13. The method of producing a colored photographic image in a gelatino-silver halide emulsion layer which comprises coupling the development product of an aromatic amino developing compound containing a primary amino group with a compound having the formula on Y where YC-R is a structure selected from the class consisting of structures wherein Y-C-R togetherrepresent the atoms necessary to complete an organic ring selected from the class consisting of heterocyclic rings and carbocyclic rings, and structures wherein Y represents a hydrogen atom and 13. represents an organic ring selected from the class consisting of heterocyclic rings and aromatic rings.

it. The method of producing a colored photographic image in a gelatino-silver halide emulsion layer which comprises coupling the development product of an aromatic amino developing compound containing a primary amino group with a compound present in the developer having the formulawhere YC--R is a structure selected from the class consisting of structures wherein Y--C-R. together represent the atoms necessary to complete an organic ring selected from the class consisting of heterocyclic rings and carbocyclic rings, and structures wherein Y represents a hydrogen atom and R represents an organic ring selected from the class consisting of'heterocyclic rings and aromatic rings.

15. The method of producing a colored photographic image in a gelatino-silver halide emulsion layer which comprises coupling the development product of an aromatic amino developing compound containing a primary amino group with a compound present in the emulsion layer having the formula 

